JP2016500400A - Thermoplastic composition - Google Patents

Abstract

The present invention comprises: a) a1) a thermoplastic resin, a2) a silicon-containing rubber and / or b) a polysiloxane-polycarbonate copolymer; c) a BET surface area measured according to DIN ISO 9277: 2010 of at least 10. The present invention relates to a thermoplastic composition containing a metal (oxy) hydroxide.

Description

  The present invention relates to a thermoplastic composition which is impact resistant and flame retardant and to a product made from said composition. The invention also relates to the use of said composition in a laser direct structuring process.

A thermoplastic composition having impact resistance and flame retardancy is described in, for example, EP 2336247. EP 2336247 discloses at least a polycarbonate resin (A), an organic sulfonic acid metal salt (B), a fluoropolymer (C), and polyalkylsilsesquioxane particles (D) having an average particle size of 0.6 to 5 μm. And a polycarbonate resin composition containing a graft copolymer (E) having a butadiene content of 50% or more. European Patent No. 2336247 states that this composition has very high flame retardancy and is excellent in impact resistance and surface appearance.
U.S. Pat. No. 7,985,788 discloses a flame retardant resin composition containing a polyalkylene flange carboxylate, an aromatic polycarbonate, a phosphazene compound, a fluorine-containing compound, and a silicone / acrylic core-shell rubber. US 7985788 states that this composition is excellent in both impact resistance and flame retardancy.

WO1110365 pamphlet describes (i) an aromatic polycarbonate or aromatic polyester carbonate, (ii) a silicon-free graft (co) polymer produced by bulk polymerization, and (iii) a silicon-containing graft having a core-shell morphology. (Vi) a polymer, (iv) an oligomeric aromatic phosphorus compound, (v) a polytetrafluoroethylene polymer, a fluorothermoplast, or a mixture thereof, (vi) a thermoplastic vinyl (co) polymer, (iii) Disclosed is an ignition resistant carbonate polymer composition comprising at least one of impact modifiers, fillers, reinforcing materials, stabilizers, pigments, dyes, mold release agents, lubricants, or antistatic agents. ing. WO1110365 pamphlet states that this composition is excellent in ignition resistance, in particular, has a short combustion time, good mechanical properties, and high heat resistance.
WO09024496 pamphlet includes a) 30 to 97% by mass of aromatic polycarbonate, b) 0.5 to 20% by mass of a metal compound that can be activated by electromagnetic radiation to form a metal element nucleus, and c) at least Disclosed is a polymer composition containing 2.5 to 50% by weight of a single rubber-like polymer, where the sum of a) to c) is 100%. Examples of the rubber include siloxane rubber. Provided is a polymer composition that can be used in a laser direct structuring method and suppresses decomposition of an aromatic polycarbonate.
While known compositions are satisfactory in some circumstances, there remains a need for thermoplastic compositions that exhibit good flame retardancy and good impact strength.

European 2336247 US 7985788 WO1110365 pamphlet WO09024496 pamphlet

  The object of the present invention is to provide a thermoplastic composition exhibiting good flame retardancy and good impact strength.

The purpose is to make the thermoplastic composition
a) a1) a thermoplastic resin and a2) a Si-containing rubber and / or b) a polysiloxane-polycarbonate copolymer;
c) achieved by containing a metal (oxy) hydroxide having a BET surface area measured according to DIN ISO 9277: 2010 of at least 10.
Said thermoplastic composition contains components a) and c), b) and c), or a), b) and c).

Surprisingly, when the Si-containing component and the metal (oxy) hydroxide are used in combination, that is, when the components a2) and c) or b) and c) are used together, good flame retardancy and good impact strength are obtained. Turned out to be.
Improving the impact strength of a thermoplastic composition generally significantly reduces flame retardancy. When the Si component is used as the impact resistance improver, the reduction in flame retardancy can be suppressed as compared with the case where other types of impact resistance improvers such as butadiene are added. However, the flame retardant property of the composition improved in impact strength by using the Si component is still lower than that of the composition not using rubber.
Surprisingly, high flame retardancy was obtained by adding a metal (oxy) hydroxide having a BET surface area of at least 10 to a composition containing a Si component as an impact modifier. It has been found that metal (oxy) hydroxide dimensions are an important factor in achieving improved flame retardancy.
Good weatherability / ultraviolet resistance was also observed in the compositions of the present invention.
The use of a metal hydroxide in a flame retardant polycarbonate composition containing a phosphorus flame retardant is described in EP 2468820. EP 2468820 states that this composition also exhibits good flowability as well as improved flame retardancy. However, European 2468820 does not mention the BET surface area of the metal hydroxide.

The total ratio of a) and b) with respect to the whole composition is preferably 75 to 99% by weight. The ratio of a) to the sum of a) and b) is 0 to 100 wt%, 1 to 99 wt%, 5 to 95 wt%, 10 to 90 wt%, 25 to 75 wt%, or 40 to 60 wt%. be able to.
The total ratio of a1) and b) to the whole composition is preferably 75 to 99% by weight. The ratio of a1) to the sum of a1) and b) is 0 to 100% by weight, 1 to 99% by weight, 5 to 95% by weight, 10 to 90% by weight, 25 to 75% by weight, or 40 to 60% by weight. be able to.

Properties Preferably, the molded part of the composition is 1.6 mm thick and is UL94 grade V2, preferably grade V1, more preferably grade V0. More preferably, the molded sample of the composition is 0.8 mm thick and is grade V2, preferably grade V1, more preferably grade V0.
UL94V is a method for evaluating flame retardancy from afterflame time and drip characteristics. A sample piece of a predetermined size for the UL test can be maintained in a room under temperature control to evaluate flame retardancy.
The composition of the present invention has good hydrolysis stability. Preferably, after a hydrolysis exposure test, the composition is placed in an autoclave and treated at a temperature of 120 ° C., 100% relative humidity and a pressure of 2 bar for 50 hours, and the composition is dried in a vacuum-N ₂ oven at 120 ° C. for 4 hours. A melt flow index (MFI) measured in accordance with ISO 1133 under a load of 1.2 kg at a melting temperature of 300 ° C. is defined as a second melt flow index, and 1. at a melting temperature of 300 ° C. before the hydrolysis exposure test. When the melt flow index (MFI) measured according to ISO 1133 under a load of 2 kg is used as the first melt flow index, the composition of the present invention has the second melt flow index (MFI) and the first melt flow. The index (MFI) ratio is at most 3, preferably at most 2.5, more preferably at 2.0
The composition of the present invention has a large impact strength value, for example, expressed as notched Izod impact strength. Preferably, the notched Izod impact strength (measured according to ISO 180 / 4A at a sample thickness of 3.2 mm) of a molded part of the thermoplastic composition at −20 ° C. is a value higher than 25 kJ / m ^2. . Preferably, the notched Izod impact strength (measured according to ISO 180 / 4A at a sample thickness of 3.2 mm) of the molded part of the thermoplastic composition at room temperature is a value higher than 40 kJ / m ² .

Ingredient a)
In certain preferred embodiments, the thermoplastic composition contains a1) a thermoplastic resin and a2) a Si-containing rubber. Thermoplastic resin is used as the main component of the composition, and Si-containing rubber is added as an impact resistance improver for the thermoplastic resin. The thermoplastic composition may or may not further contain b) a polysiloxane-polycarbonate copolymer.
The present inventor reduces the hydrolysis stability of the composition when Si-containing rubber is added to the thermoplastic resin. However, when component c) is added, this decrease in hydrolysis resistance due to the addition of Si-containing rubber is reduced. I found it to be minimal.

Component a1)
The concentration of the thermoplastic resin a1) in the composition of the present invention is preferably from 50% to 98% by weight, more preferably from 70% to 97% by weight, based on the weight of the entire composition.
Examples of thermoplastic resins that can be included in the composition of the present invention include, but are not limited to, polycarbonates, particularly aromatic polycarbonates, polyamides, polyesters, polyesteramides, polystyrenes, polymethylmethacrylates or combinations of such resins. Is mentioned. The resin may be a homopolymer, a copolymer or a mixture thereof, and may be branched or unbranched. Of course, the thermoplastic resin a2) does not contain polysiloxane-polycarbonate.
Examples of suitable polyamides (PA) are aliphatic polyamides such as PA6, PA46, PA66, PA6 / 66, PA11, PA12, which may optionally be branched polyamides, half of MXD6, PA6I / 6T, PA66 / 6T, PA4T, etc. Aromatic polyamides, wholly aromatic polyamides and copolymers and blends of the above polyamides. Examples of suitable polyesters are polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polyethylene naphthanoate (PEN), polybutylene naphthanoate (PBN). Preferred polyesters are polyethylene terephthalate and polybutylene terephthalate.
In a preferred embodiment, the thermoplastic resin includes a polycarbonate resin. The polycarbonate-based resin can be selected from polycarbonate or a resin blend containing polycarbonate. The polycarbonate may be a homopolymer, a copolymer or a mixture thereof, and may be branched or unbranched. Suitable polycarbonate resins are described, for example, in US 2009/0292048, which is incorporated herein by reference.
Polycarbonates containing aromatic carbonate chain units can be represented by the formula (I):
—R ¹ —O—CO—O— (I)
In the above formula, the R ¹ group is an aromatic, aliphatic or alicyclic group. R ¹ is advantageously an aromatic organic group, and in another embodiment the formula (II):
-A ¹ -Y ¹ -A ^2- (II)
In the above formula, each of A ¹ and A ² is a monocyclic divalent aryl group, and Y ¹ is a bridging group having 0, 1, or 2 atoms that separates A ¹ from A ^2. is there. In an exemplary embodiment, the number of atoms separating A ¹ from A ² is 1. Specific examples of this type of group include —O—, —S—, —S (O) —, —S (O ₂ ) —, —C (O) —, methylene, cyclohexylmethylene, 2- [2,2, 1] -bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, adamantylidene, and the like. In another embodiment, the number of atoms separating A ¹ from A ² is 0, an example being bisphenol. The bridging group Y ¹ can be a hydrocarbon group such as methylene, cyclohexylidene or isopropylidene or a saturated hydrocarbon group.
Suitable aromatic polycarbonates include, for example, polycarbonates made from at least divalent phenols and carbonate precursors by well-known interfacial polymerization or melt polymerization methods. Suitable divalent phenols that can be used are compounds having one or more aromatic rings containing two hydroxy groups each directly bonded to the carbon atoms that make up the aromatic ring. Examples of such compounds are 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis- (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2 -Methylbutane, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 4,4-bis (4-hydroxyphenyl) heptane, bis (3,5-dimethyl-4-hydroxy- -Phenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) si Rhohexane, 2,2- (3,5,3 ′, 5′-tetrachloro-4,4′-dihydroxydiphenyl) propane, 2,2- (3,5,3 ′, 5′-tetrabromo-4,4 '-Dihydroxydiphenyl) propane, (3,3'-dichloro-4,4'-dihydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis-4-hydroxyphenylsulfone, bis- 4-hydroxyphenyl sulfide.
Examples of the carbonate precursor include carbonyl halide, halogenated formate, and carbonate. Examples of carbonyl halides are carbonyl chloride and carbonyl bromide. Examples of suitable halogenated formates are bishalogenated formates of dihydric phenols such as hydroquinone and glycols such as ethylene glycol. Examples of suitable carbonates are diphenyl carbonate, di (chlorophenyl) carbonate, di (bromophenyl) carbonate, di (alkylphenyl) carbonate, phenyltolyl carbonate and the like and mixtures thereof. Other carbonate precursors may be used, but it is preferred to use carbonyl halides, particularly carbonyl chloride (also known as phosgene).
The aromatic polycarbonate in the composition of the present invention can be produced using a catalyst, an acid acceptor, and a molecular weight adjusting compound.
Examples of catalysts are tertiary amines such as triethylamine, tripropylamine and N, N-dimethylaniline, quaternary ammonium compounds such as tetraethylammonium bromide, and quaternary phosphonium compounds such as methyltriphenylphosphonium bromide. is there.
Examples of organic acid acceptors are pyridine, triethylamine, dimethylaniline and the like. Examples of inorganic acid acceptors are alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates and phosphates.
Examples of the molecular weight adjusting compound are monovalent phenols such as phenol, p-alkylphenol and parabromophenol, and secondary amines.

Component a2)
Component a2) is preferably a graft copolymer containing an elastomer component containing Si. The graft copolymer is formed by graft copolymerizing an Si-containing elastomer component with a monomer component copolymerizable therewith. The elastomer component generally has a maximum glass transition temperature of 0 ° C., preferably −20 ° C., more preferably −30 ° C.
The graft copolymer used in the present invention is preferably a core-shell type graft copolymer having an Si-containing elastomer component as a core. Polyorganosiloxane is preferable as the elastomer component containing Si.
Component a2) is, for example, as described in US 2005/0143520, in the presence of 40 to 95 parts by weight of polyorganosiloxane particles (II), and vinyl monomer (I) 5 to 60 parts by weight. A polyorganosiloxane-containing graft copolymer that is preferably produced by polymerizing parts (100 parts by weight in total of (I) and (II)) is preferred. Examples of the vinyl monomer (I) include, for example, aromatic vinyl monomers such as styrene, α-methyl styrene, paramethyl styrene and parabutyl styrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. Monomer: methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid (Meth) acrylic acid ester monomers such as butyl, lauryl methacrylate, glycidyl methacrylate, and hydroxyethyl methacrylate; and vinyl group-containing vinyl compounds such as itaconic acid, (meth) acrylic acid, fumaric acid, and maleic acid Monomer listed It is. The vinyl monomer (a-1) may contain a polyfunctional monomer containing at least two polymerizable unsaturated bonds per molecule, if necessary. Examples of the polyfunctional monomer include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and divinylbenzene. . The vinyl monomer (I) may be used alone or in combination of two or more. The polyorganosiloxane particles (II) are preferably produced by emulsion polymerization of the constituent components. Normal graft emulsion polymerization can be applied to the graft copolymerization, and can be carried out by radical polymerization of the vinyl monomer (I) in the latex of the polyorganosiloxane particles (II).
For example, Kaneace MR01 and Kaneace MR02 are commercially available from Kaneka Corporation as these graft copolymers containing polyorganosiloxane.
Other materials suitable as component a2) include Metablene S-2001, Metabrene S-2200, and Metabrene SX05 from Mitsubishi Rayon.
Preferably, the thermoplastic composition contains 1 to 20 wt% Si-containing rubber, preferably 2 to 15 wt%, more preferably 3 to 10 wt%. The thermoplastic composition of the present invention is preferably substantially free of other types of rubber, particularly butadiene rubber.

Component b):
The thermoplastic composition may contain a polysiloxane-polycarbonate copolymer as a main component of the composition. In the thermoplastic resin a1), the impact strength is improved by the Si-containing rubber a2). However, in the polysiloxane-polycarbonate copolymer, the impact strength is improved by the presence of a polysiloxane block in the copolymer. Yes. Examples of the polysiloxane-polycarbonate copolymer are described in, for example, US Pat. No. 5,380,795 and WO 09/040772, which are incorporated herein by reference, and are as follows.
The polysiloxane (also known as “polydiorganosiloxane”) block of the copolymer has the formula (1):
In the above formula, each R is the same or different and is a monovalent organic group having 1 to 13 carbon atoms. For example, R is independently _C 1 _{-C 13} alkyl _groups, C 1 _{-C 13} alkoxy _groups, C 2 _{-C 13} alkenyl _groups, C 2 _{-C 13} alkenyloxy _group, C 3 -C ₆ cycloalkyl groups, C _3- C ₆ cycloalkoxy group, C ₆ -C ₁₄ aryl group, C ₆ -C ₁₀ aryloxy group, C ₇ -C ₁₃ arylalkyl group, C ₇ -C ₁₃ arylalkoxy group, C ₇ -C ₁₃ alkylaryl Or a C ₇ -C ₁₃ alkylaryloxy group. The above groups may be all or partly halogenated with fluorine, chlorine, bromine or iodine or a combination thereof. Combinations of the above R groups can be used in the same copolymer.
The numerical value of E in formula (1) can take a wide range depending on factors such as the type and relative amount of each component in the thermoplastic composition, and desirable properties of the composition. In general, E can have an average value of 2 to 1,000, specifically 2 to 500, more specifically 5 to 100. In one embodiment, E has an average value of 10-75, and in yet another embodiment, E has an average value of 20-60. When the value of E is small, for example, less than 40, it may be desirable to use Si-containing rubber in combination, and it may be desirable to use a large amount in combination. For example, the composition containing the polysiloxane-polycarbonate copolymer may contain a small amount of the thermoplastic resin and a large amount of the Si-containing rubber. On the contrary, when the value of E is large, for example, when it exceeds 40, the composition containing the polysiloxane-polycarbonate copolymer may contain a large amount of the thermoplastic resin and a small amount of the Si-containing rubber. Seems desirable.
The first and second (or three or more) polysiloxane-polycarbonate copolymers are prepared so that the average value of E of the first copolymer is smaller than the average value of E of the second copolymer. You may use together.
In one embodiment, the polydiorganosiloxane block has the formula (2):
Wherein E is as defined above; R may be independently the same or different, and is as defined above; Ar is independently the same or different. It may be a substituted or unsubstituted C ₆ -C ₃₀ arylene group, and the bond is directly linked to the aromatic moiety. Ar groups useful in Formula (2) can be derived from a C ₆ -C ₃₀ dihydroxyarylene compound, for example, dihydroxy arylene compound. Combinations containing at least one of the above dihydroxyarylene compounds can also be used. Specific examples of the dihydroxyarylene compound include 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl sulfide), and 1,1-bis (4-hydroxy- t-butylphenyl) propane. Combinations containing at least one of the above dihydroxy compounds can also be used.
The unit of the formula (2) is the formula (3):
Wherein R, Ar, and E are as defined above. The compound of the formula (3) can be obtained by reacting a dihydroxyarylene compound with, for example, α, ω-bisacetoxypolydiorganosiloxane under phase transition conditions.
In another embodiment, the polydiorganosiloxane block has the formula (4):
Wherein R and E are as defined above, each R is independently a C ₁ -C ₃₀ divalent alkylene group, and the polymerized polysiloxane unit is the reaction of its corresponding dihydroxy compound. Residue. In one particular embodiment, the polydiorganosiloxane block has the formula (5):
Wherein R and E are as defined above. R ⁵ in the formula (5) is each independently a C ₂ -C ₈ divalent aliphatic group. M in the formula (5) may be the same or different, and is halogen, cyano group, nitro group, C ₁ -C ₈ alkylthio group, C ₁ -C ₈ alkyl group, C ₂ -C ₈ alkoxy group, C _2. -C _{8 alkenyl,} C 2 -C ₈ alkenyloxy _group, C 3 -C ₈ cycloalkyl _group, C 3 -C ₈ cycloalkoxy _group, C 6 _{-C 10} aryl _group, C 6 _{-C 10} aryloxy group, C ₇ -C ₁₂ arylalkyl _group, C 7 _{-C 12} arylalkoxy _group, C 7 _{-C 12} alkylaryl group, or a _C 7 _{-C 12} may be a alkyl aryl radical, n are each independently 0 , 1, 2, 3, or 4.
In one embodiment, M is an alkyl group such as bromo group or chloro group, methyl group, ethyl group or propyl group, alkoxy group such as methoxy group, ethoxy group or propoxy group, or phenyl group, chlorophenyl group or tolyl group. R ⁵ is a dimethylene group, trimethylene group or tetramethylene group; R is a haloalkyl group such as a Ci_s alkyl group or a trifluoropropyl group, a cyanoalkyl group, a phenyl group, a chlorophenyl group or a tolyl group An aryl group. In another embodiment, R is a methyl group, or a mixed group of a methyl group and a trifluoropropyl group, or a mixed group of a methyl group and a phenyl group. In yet another embodiment, M is a methoxy group, n is 1, R ⁵ is a C ₁ -C ₃ divalent aliphatic group, and R is a methyl group.
The unit of formula (5) is the corresponding dihydroxypolydiorganosiloxane (6):
Wherein R, E, M, R ⁵ , and n are as defined above. Such dihydroxypolysiloxanes have the formula (7):
(Wherein, R and E have the same meanings as described above) can be produced by carrying out a platinum-catalyzed addition reaction of a hydrogenated siloxane and an aliphatic unsaturated monovalent phenol. Useful aliphatic unsaturated monovalent phenols include, for example, eugenol, 2-allylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, A -Allyl-2-t-butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methyl Examples include phenol, 2-allyl-6-methoxy-4-methylphenol and 2-allyl-4,6-dimethylphenol. Mixtures containing at least one of the above can also be used.

In an exemplary embodiment, the polysiloxane block is a poly (dimethylsiloxane) (PDMS) block.
The polysiloxane-polycarbonate may contain 85 to 99% by weight of carbonate units and 1 to 15% by weight of siloxane units. Within this range, the polysiloxane-polycarbonate copolymer is 88%, 90%, 92%, 94%, 96%, or 98% by weight of carbonate units, correspondingly 2% by weight of siloxane units. %, 4%, 6%, 8%, 10%, or 12% by weight. In one particular embodiment, the polysiloxane-polycarbonate comprises 85-98 wt% carbonate units and 2-15 wt% siloxane units. In another specific embodiment, the polysiloxane-polycarbonate comprises 90-98 wt% carbonate units and 2-10 wt% siloxane units.
In one embodiment, the polysiloxane-polycarbonate may include polysiloxane units and carbonate units derived from bisphenol A. When measured by gel permeation chromatography at a sample concentration of 1 mg / ml using a crosslinked styrene-divinylbenzene column and calibrated with a polycarbonate standard, the polysiloxane-polycarbonate has a weight average molecular weight of 2,000-100. 5,000, specifically 5,000 to 50,000.
The polysiloxane-polycarbonate has a melt volume flow rate measured at 300 ° C. under a load of 1.2 kg, 1 to 50 cm ³ (cc / 10 minutes) per 10 minutes, specifically 2 to ³⁰ cc / 10 minutes. be able to. Polysiloxane-polycarbonate mixtures with different flow properties can be used to achieve the desired total flow properties. In one embodiment, a typical polysiloxane-polycarbonate is commercially available from Sabic Innovative Plastics under the trade name LEXAN® EXL polycarbonate.
In one embodiment, the thermoplastic composition is 2 wt% or less, specifically 0.1 to 2 wt%, more specifically 0.1 to 1. wt% relative to the total weight of the thermoplastic composition. It contains siloxane units of the formula (1) in an amount of 5% by weight, more particularly 0.1 to 1.0% by weight.
When the value of E is small, for example, less than 40, the weight ratio of component (b) to the sum of components (a1) and (b) may be at least 50%, for example, or 100%. For example, the composition comprises (a1) 0 to 50% by weight of the thermoplastic resin, (a2) 1 to 20% by weight of the Si-containing rubber, and (b) 50 to 99% by weight of the polysiloxane-polycarbonate copolymer. Can be contained.
When the value of E is small, for example less than 40, the weight ratio of component (b) to the sum of components (a1) and (b) is preferably less than 50%, for example. For example, the composition comprises (a1) 50 to 98% by weight of the thermoplastic resin, (a2) 1 to 20% by weight of the Si-containing rubber, and (b) 1 to 49% by weight of the polysiloxane-polycarbonate copolymer. Can be contained.

Component c)
In this application, the term metal (oxy) hydroxide shall mean both metal hydroxide and metal oxyhydroxide.
The metal (oxy) hydroxide is preferably a compound represented by the general formula M _a (OH) _b or M _a O (OH) _b , wherein M is Li, Na, K, Mg, Selected from the group consisting of Ca, Al, Zn, and Fe, a is 1 or 2, and b is 1, 2 or 3. M is preferably Mg or Al. Since metal (oxy) hydroxide mainly composed of Al has high temperature stability, M is most preferably Al.
The metal (oxy) hydroxide is preferably a metal oxyhydroxide represented by the general formula M _a O (OH) _b , wherein a is 1 or 2, and b is 1, 2 or 3. is there. Preferably, a is 1 and b is 2.
Specific examples of the metal (oxy) hydroxide include AlO (OH), Al (OH) ₃ , Mg (OH) ₂ , and Mg ₂ O (OH) ₂ . Preferably, the metal oxyhydroxide is AlO (OH), preferably γ-AlO (OH).
The metal (oxy) hydroxide preferably has a BET surface area of at least 12, more preferably at least 15.
Preferably, the thermoplastic composition contains 1 to 20 wt%, preferably 2 to 15 wt%, more preferably 3 to 10 wt% of the metal (oxy) hydroxide.
Particularly preferred examples of the thermoplastic composition of the present invention include a core-shell graft copolymer comprising polyorganosiloxane as component a2) and AlO (OH) as component c) in the core.

Component d): Flame retardant The thermoplastic composition of the present invention may further contain a flame retardant. Flame retardancy is further improved. A well-known thing is used for a flame retardant. Suitable examples of flame retardants include certain alkali or alkaline earth sulfonates (eg potassium perfluorobutane sulfonate), sulfonamides, perfluoroborate, halogenated compounds, especially brominated aromatic compounds, and phosphorus. It is an organic compound containing a phosphate ester such as triphenyl phosphate and a phosphorus-nitrogen bond, particularly a contained organic compound. Suitable phosphorus-containing compounds are described, for example, in German 1928535A1 (component E), European 0640655A2 (component D) and European 0363608A1 (component C). As the flame retardant compound, it is preferable to use a phosphorus flame retardant such as resorcinol diphenyl phosphate (RDP), bisphenol A diphenyl phosphate (BDP), triphenyl phosphate, or a mixture thereof. Phosphorus flame retardants are preferred because flame retardancy is significantly improved when used in combination with metal hydroxides.
The thermoplastic composition preferably contains 0 to 15% by weight of flame retardant d). A more suitable range of the amount of flame retardant is 0.1 to 10% by weight or 1 to 5% by weight.

Ingredient e): Colorant / LDS additive In certain embodiments, the composition further comprises e) copper-containing spinels such as copper chromium oxide spinel, copper molybdenum oxide spinel and copper chromium manganese oxide spinel; and tin antimony Contains an additive selected from tin-containing oxides such as oxide, tin bismuth oxide, tin aluminum oxide and tin molybdenum oxide.
These additives can function, for example, as pigments. In addition to or instead of the above, these additives may be used as laser direct structuring (LDS) additives.
The terms “laser direct structuring additive” or “LDS additive” are known and used in, for example, European 2291290B1, US2005064711, WO2005 / 103113 pamphlet and WO2009 / 024496 pamphlet. In the laser direct structuring method, a thermoplastic composition containing a thermoplastic resin and a laser direct structuring additive is prepared, and the region of the thermoplastic composition where a conductive path is to be formed is irradiated with laser light. Subsequently, the irradiated region is selectively metallized to form a conductive path. Metallization does not occur in areas not irradiated with laser light. The metallization can be performed by a standard electroless plating method such as a copper plating method.
Without being bound by theory, it is believed that the laser direct structuring additive can be activated by laser light to form metal element particles. These metal particles act as the core of copper deposition by the standard electroless copper plating method, and are considered to be the basis for the formation of conductive paths. It is also considered that laser light is not directly absorbed by the laser direct structuring additive, but is absorbed by another substance, and then the absorbed energy is transferred to the laser direct structuring additive to release the metal element.
As the laser light, ultraviolet light (wavelength 100 to 400 nm), visible light (wavelength 400 to 800 nm), or infrared light (wavelength 800 to 25000 nm) can be used. Other preferred radiation species are X-rays, gamma rays, and particle beams (electron beam, alpha particle beam, and beta particle beam). The laser beam is preferably infrared, and more preferably has a wavelength of 1064 nm.
As the additive, copper-containing spinels such as copper chromium oxide spinel, copper manganese oxide spinel and copper molybdenum oxide spinel can be used. The copper-containing spinel can function as a black pigment. The copper-containing spinel can also function as a laser direct structuring (LDS) additive. For this reason, the composition which has favorable impact strength and favorable flame retardance, and can be used for LDS method is obtained.

  Accordingly, the present invention relates to a) a1) a thermoplastic resin and a2) a Si-containing rubber, c) a metal (oxy) hydroxide having a BET surface area measured according to DIN ISO 9277: 2010 of at least 10, e ) A thermoplastic composition containing a copper-containing spinel is provided. The present invention further comprises b) a polysiloxane-polycarbonate copolymer, c) a metal (oxy) hydroxide having a BET surface area measured according to DIN ISO 9277: 2010 of at least 10, and e) a copper-containing spinel. A thermoplastic composition is provided.

As the additive, tin-containing oxides such as tin antimony oxide, tin bismuth oxide, tin aluminum oxide and tin molybdenum oxide can be used. The tin-containing oxide has a color ranging from almost white to light gray and can function as a pigment for imparting a corresponding color such as light gray. The tin-containing oxide can further function as a laser direct structuring (LDS) additive. It has been found that when component b) and antimony tin oxide are used in combination without adding component c), the flame retardancy and hydrolysis stability are further reduced. The addition of component c) suppresses this significant reduction in flame retardancy, and as a result, a composition that has good impact strength, good flame retardancy, and good hydrolysis stability and can be used in the LDS process. Things are obtained.
Accordingly, the present invention relates to a) a1) a thermoplastic resin and a2) a Si-containing rubber, c) a metal (oxy) hydroxide having a BET surface area measured according to DIN ISO 9277: 2010 of at least 10, e ) A thermoplastic composition containing a tin-containing oxide is provided. The present invention further includes b) a polysiloxane-polycarbonate copolymer, c) a metal (oxy) hydroxide having a BET surface area measured according to DIN ISO 9277: 2010 of at least 10, and e) a tin-containing oxide. A thermoplastic composition is provided.

The additive e) is preferably small in size so as to impart good mechanical strength to the composition of the invention.
Preferably, the additive e) has a particle size D90 of at most 10 μm, more preferably at most 8 μm. More preferably, the metal oxide has a maximum particle size D90 of 6 μm, more preferably a maximum of 4 μm, and even more preferably a maximum of 2.5 μm.
Preferably, the additive e) has a particle size D50 of at most 6 μm, more preferably at most 5 μm. More preferably, the additive e) has a particle size D50 of at most 3 μm, more preferably at most 1 μm.
The particle size can be measured by light scattering techniques using, for example, a Microtrac full range particle size analyzer (FRA) or a Malvern Mastersizer particle size analyzer.
The concentration of component e) present in the composition of the present invention is preferably 0% to 25% by weight, more preferably 1 to 20% by weight, more preferably 3% to 15% by weight relative to the weight of the entire composition. More preferred is 5 to 10% by weight.

In the component f) white pigment certain embodiments, the composition further contains a white pigment selected from _TiO 2, ZnO and BaSO _4. Thereby, a white or light-colored thermoplastic composition can be obtained. The white pigment is advantageous in that other color pigments or dyes can be added to impart the desired color, provided that the amount does not interfere with the desired properties of the composition. Other pigments and dyes for imparting the desired color to the thermoplastic composition are known to those skilled in the art and are commercially available. Known pigments include metal oxides commercially available from vendors such as Ferro, The Shepherd Color Company, Hebach, Rockwood Pigments, Tomatec, and Roll-Buntpimente.
It has been found that when the impact resistance improver and TiO ₂ are used in combination, the reduction in flame retardancy is greater. For this reason, obtaining a white or light-colored composition with good flame retardancy is more difficult than obtaining a black or dark-colored composition with good flame retardancy. Addition of component b) suppresses this significant reduction in flame retardancy, resulting in a desired color composition with good impact strength and good flame retardancy.
Accordingly, the present invention relates to a) a1) a thermoplastic resin and a2) a Si-containing rubber, c) a metal (oxy) hydroxide having a BET surface area measured according to DIN ISO 9277: 2010 of at least 10, f ) A thermoplastic composition containing TiO 2 is provided. The present invention further comprises b) a polysiloxane-polycarbonate copolymer, c) a metal (oxy) hydroxide having a BET surface area measured according to DIN ISO 9277: 2010 of at least 10, and f) TiO ₂ . A thermoplastic composition is provided. The present invention further comprises a) a1) a thermoplastic resin and a2) a Si-containing rubber, c) a metal (oxy) hydroxide having a BET surface area measured according to DIN ISO 9277: 2010 of at least 10, and e) A thermoplastic composition comprising an additive selected from a copper-containing spinel and a tin-containing oxide and f) TiO 2 is provided. The present invention further includes b) a polysiloxane-polycarbonate copolymer, c) a metal (oxy) hydroxide having a BET surface area of at least 10 measured according to DIN ISO 9277: 2010, e) a copper-containing spinel, and There is provided a thermoplastic composition comprising an additive selected from tin-containing oxides and f) TiO ₂ .
The concentration of component f) present in the composition of the present invention is preferably 0% to 25% by weight, more preferably 0.1 to 20% by weight, more preferably 0.5% to 10 wt% is more preferable, and 1 wt% to 5 wt% is particularly preferable.

Other Additives The thermoplastic composition of the present invention may further contain 0 to 25% by weight of one or more other additives based on the total weight of the composition. These additives include thermal or thermal oxidative degradation stabilizers, hydrolysis stabilizers, stabilizers for degradation and / or photo-oxidative degradation due to light, especially UV rays, anti-dripping agents (eg PTFE), processing aids (eg release agents). Conventional additives such as molds and lubricants) and colorants (eg pigments and dyes). Suitable examples of such additives and their general addition amounts are described in Kunststoff Handbuch, 3/1 above.
Preferably, the sum of a) to f) is at least 90%, at least 95%, at least 98% or at least 99% by weight of the total composition. The sum of a) to f) may be 100% by weight of the total composition.

In a preferred embodiment, the composition of the present invention comprises
a) a1) 50 to 98% by weight of thermoplastic resin, a2) 1 to 20% by weight of Si-containing rubber,
b) 0 to 48% by weight of a polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 0-25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) Contains 0 to 25% by weight of white pigment.
In a further preferred embodiment, the composition of the present invention comprises
a) a1) thermoplastic resin 0-49 wt%, a2) Si-containing rubber 0-20 wt%,
b) 50 to 99% by weight of a polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 0-25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) Contains 0 to 25% by weight of white pigment.
In a further preferred embodiment, the composition of the present invention comprises
a) a1) 1 to 98% by weight of thermoplastic resin, a2) 1 to 20% by weight of Si-containing rubber,
b) 1 to 97% by weight of a polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 0-25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) containing 0 to 25% by weight of a white pigment,
The sum of a1) and b) is 50 to 99% by weight of the total composition.
In a preferred embodiment, the composition of the present invention comprises
a) a1) 50 to 97% by weight of thermoplastic resin, a2) 1 to 20% by weight of Si-containing rubber,
b) 0 to 47% by weight of a polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 1 to 25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) Contains 0 to 25% by weight of white pigment.

In a further preferred embodiment, the composition of the present invention comprises
a) a1) 0 to 48% by weight of thermoplastic resin, a2) 0 to 20% by weight of Si-containing rubber,
b) 50 to 98% by weight of a polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 1 to 25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) Contains 0 to 25% by weight of white pigment.
In a further preferred embodiment, the composition of the present invention comprises
a) a1) 1 to 97% by weight of thermoplastic resin, a2) 1 to 20% by weight of Si-containing rubber,
b) 1 to 96% by weight of a polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 1 to 25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) containing 0 to 25% by weight of a white pigment,
The sum of a1) and b) is 50 to 97% by weight of the total composition.
In a preferred embodiment, the composition of the present invention comprises
a) a1) 50 to 97% by weight of thermoplastic resin, a2) 1 to 20% by weight of Si-containing rubber,
b) 0 to 47% by weight of a polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 0-25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) Contains 1 to 25% by weight of white pigment.
In a further preferred embodiment, the composition of the present invention comprises
a) a1) 0 to 48% by weight of thermoplastic resin, a2) 0 to 20% by weight of Si-containing rubber,
b) 50 to 98% by weight of a polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 0-25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) Contains 1 to 25% by weight of white pigment.

In a further preferred embodiment, the composition of the present invention comprises
a) a1) 1 to 97% by weight of thermoplastic resin, a2) 1 to 20% by weight of Si-containing rubber,
b) 1 to 96% by weight of a polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 0-25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) containing 1 to 25% by weight of white pigment,
The sum of a1) and b) is 50 to 97% by weight of the total composition.
In a preferred embodiment, the composition of the present invention comprises
a) a1) 50 to 96% by weight of thermoplastic resin, a2) 1 to 20% by weight of Si-containing rubber,
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 1 to 25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) Contains 1 to 25% by weight of white pigment.
In a further preferred embodiment, the composition of the present invention comprises
a) a1) thermoplastic resin 0-47 wt%, a2) Si-containing rubber 0-20 wt%,
b) 50 to 97% by weight of a polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 1 to 25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) Contains 1 to 25% by weight of white pigment.
In a further preferred embodiment, the composition of the present invention comprises
a) a1) 1 to 96% by weight of thermoplastic resin, a2) 1 to 20% by weight of Si-containing rubber,
b) 1 to 95% by weight of a polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 1 to 25 wt% additive selected from copper-containing spinel and tin-containing oxide;
f) containing 1 to 25% by weight of white pigment,
The sum of a1) and b) is 50 to 96% by weight of the total composition.

  Of course, the description of the present application discloses the above various compositions in which the amount of each component is in the range described as being preferable in the section relating to the details of each component.

The above components a) to f) and other additives may be mixed by a suitable mixing device such as a single screw or twin screw extruder, and it is preferable to use a twin screw extruder. Therefore, the present invention further relates to a method for producing the thermoplastic composition of the present invention by melt mixing components a) to c) and other components.
The invention further relates to a molded part comprising the thermoplastic composition of the invention. The invention particularly relates to a molded part produced by injection molding of the composition of the invention.
Examples of the molded article include electrical / electronic equipment parts, OA equipment parts, information terminal equipment parts, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods / miscellaneous goods, lighting equipment, instruments, and the like. Among these, in particular, the molded product is suitably used for parts such as electric / electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment, and particularly suitably used for electrical / electronic equipment parts.
Examples of electrical and electronic equipment include display devices such as personal computers, game machines, and televisions, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, calculators, electronic dictionaries, cameras, video cameras, mobile phones, battery packs, Examples include a recording medium driving device and a reading device, a mouse, a numeric keypad, a CD player, an MD player, and a portable radio / audio player.
The molded product can be produced by any known method. Examples include injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist molding methods, molding methods using heat insulating molds, and rapid heating molds. Molding method, foam molding method (including supercritical fluid), insert molding method, IMC (in-mold coating) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding Law. Moreover, the shaping | molding method using a hot runner system can also be utilized.

The invention further relates to a product, in particular a circuit board, comprising a molded part produced from a composition according to the invention containing a component which functions as an LDS additive as described above. In one embodiment, such a circuit board is used to manufacture an antenna.
The invention further relates to a method of manufacturing such a circuit board, the method comprising the steps of preparing a molded part comprising the thermoplastic composition of the invention and a laser in the region of the part where the conductive path is to be formed. A step of irradiating with light, and subsequently a step of metallizing the irradiated region. In a preferred embodiment, laser ablation is used to release metal nuclei while forming an adhesion promoting surface while simultaneously ablating the part. In this way, it is possible to easily achieve excellent adhesive strength for the deposited metal conductive path. The laser wavelength is advantageously 248 nm, 308 nm, 355 nm, 532 nm, 1064 nm, or even 10600 nm. In order to further deposit metal on the metal core generated by the laser beam, it is preferable to use a plating method. The metallization is preferably carried out by immersing the molded part in at least one electroless plating bath to form a conductive path in the irradiated area of the molded part. Non-limiting examples of the electroless plating method include a copper plating method, a gold plating method, a nickel plating method, a silver plating method, a zinc plating method, and a tin plating method.

Another aspect of the present invention relates to the thermoplastic composition for use in a laser direct structuring process.
The present invention further provides a metal (oxy) water having a BET surface area of at least 10 measured according to DIN ISO 9277: 2010 for improving flame retardancy in a thermoplastic composition containing a thermoplastic resin and a Si-containing rubber. Relates to the use of oxides.
The invention further relates to the use of metal (oxy) hydroxides for improving the hydrolytic stability in thermoplastic compositions containing thermoplastic resins and Si-containing rubbers. The present invention further relates to a metal (oxy) having a BET surface area of at least 10 measured according to DIN ISO 9277: 2010 for improving the hydrolytic stability of a thermoplastic composition comprising a thermoplastic resin and a Si-containing rubber. Relates to the use of hydroxides.

While the present invention has been described in detail for purposes of illustration, it will be appreciated that the above detailed description is only for this purpose, and does not depart from the spirit and scope of the invention described in the claims. Changes can be made by those skilled in the art.
Furthermore, the invention also relates to all possible combinations of the components described in the present application, with the combination of components described in the claims being particularly preferred. In particular, the invention relates to all possible combinations of elements within the scope described herein.
Further, the term “comprising” does not exclude the presence of other elements. However, as a matter of course, a description relating to a product including a predetermined element also discloses a product including these elements. Similarly, as a matter of course, the description relating to the method including the predetermined steps also discloses a method constituted by these steps.
Hereinafter, the present invention will be described in more detail by way of examples and comparative experiments.

The compositions of Comparative Experiments CEx1-11 and Examples Ex1-Ex5 were prepared from the components as shown in Table 1. In addition, processing and stabilization additives were also added. These additives include mold release agents (Cognis product Loxiol P861 / 3.5) and heat stabilizers (BASF product Irgafos 168).

Table 2 shows the specific properties of the metal hydroxide material used. The BET of the metal hydroxide particles was measured according to DIN ISO 9277: 2010. The metal hydroxide materials indicated as AlOOH1 and AlOOH2 were the same materials except that the surface coating was applied to AlOOH2, and the flame retardancy of the compositions of the examples was not affected. Similarly, the metal hydroxide materials indicated as AlOOH3 and AlOOH4 were the same materials except that the surface coating was applied to AlOOH4 and did not affect the flame retardancy of the compositions of the examples.
The particle size distribution values (D10, D50 and D90) are measured values by the manufacturer. According to the manufacturer's information, the Malvern Mastersizer particle size analyzer 2000 is used to measure the particle size distribution of the materials AlOOH 1-4.

All sample compositions were prepared according to the amounts shown in Tables 3-7. All amounts are expressed in weight percent. In each of the experiments, the sample was extruded at a temperature of 280 ° with a co-rotating twin screw extruder. Granulate the extrudate, collect the granulate and dry at 110 ° C for 4 hours, then inject into a 127 x 12.7 x 1.6 mm UL test bar using a melt temperature of about 290 ° C to 300 ° C Molded.
Flame retardancy was measured according to UL94 test method.
Hydrolysis of the compound by measuring the melt flow index (MFI) of the material before and after the hydrolysis exposure test (HT) where the granular material was placed in an autoclave and treated for 50 hours at 120 ° C., 100% relative humidity and 2 bar pressure. Stability was determined. MFI was measured according to ISO 1133 under a load of 1.2 kg at a melting temperature of 300 ° C. Prior to the MFI test, the granulate was dried in a vacuum-N2 oven at 120 ° C. for 4 hours.

Examples 1-5 and comparative experiments 1-7
In Table 3, CEx1, CEx2, CEx3, Ex1 and Ex2 show the effect of AlOOH in the PC composition containing Si rubber, titanium dioxide and ATO. Comparing CEx1 with CEx2 and CEx3, it is clear that the larger dimension AlOOH does not improve the flame retardancy of the composition, and comparing CEx1 with Ex1 and Ex2, the smaller dimension AlOOH improves the flame retardancy of the composition. It is clear that there is a marked improvement. It is also clear that differences in AlOOH grades do not substantially lead to differences in flame retardancy. Comparing CEx1 with CEx2, CEx3, Ex1 and Ex2, it is clear that the hydrolytic stability of the composition without the addition of AlOOH is significantly improved by the addition of AlOOH. In CEx1, the MFI increased 9-fold after the hydrolysis exposure test, but in the experiment in which AlOOH was added, the maximum increase in MFI was 2.2.

In Table 4, CEx4, CEx5, Ex3 and Ex4 show the effect of AlOOH in the PC composition containing Si rubber and titanium dioxide. When comparing CEx4 to CEx5, it is clear that the larger dimension AlOOH does not improve the flame retardancy of the composition, and when comparing CEx4 to Ex3 and Ex4, the smaller dimension AlOOH significantly improves the flame retardancy of the composition. It is clear to do. It is also clear that differences in AlOOH grades do not substantially lead to differences in flame retardancy. Comparing CEx4 with CEx5, Ex3 and Ex4, it is clear that the hydrolytic stability of the composition without the addition of AlOOH is significantly improved by the addition of AlOOH.

In Table 5, CEx6, CEx7 and Ex5 show the effect of AlOOH in the PC composition containing Si rubber and ATO. Comparing CEx6 with CEx7, it is clear that larger dimension AlOOH does not improve the flame retardancy of the composition, and comparing CEx6 with Ex5, the smaller dimension AlOOH significantly improves the flame retardancy of the composition Is clear.

In Table 6, CEx8 and Ex6 show the effect of AlOOH in the PC composition containing Si rubber and CuCr ₂ O ₄ . When comparing CEx8 with Ex6, it is clear that the small dimension AlOOH significantly improves the flame retardancy of the composition.
From Tables 3-6, the effect of AlOOH in PC compositions containing Si-containing rubber is evident regardless of other additives.

Table 7 shows the effect of small sized AlOOH in a PC composition containing no Si-containing rubber. Comparing CEx9 with CEx10, it is clear that small dimensions of AlOOH that improve flame retardancy in the presence of Si-containing rubber do not improve the flame retardancy of the composition. The synergistic effect of the combined use of Si-containing rubber and AlOOH is supported. Comparing CEx11 with CEx12, it is clear that flame retardancy may be reduced with AlOOH alone.

Claims (15)

a) a1) a thermoplastic resin and a2) a silicon-containing rubber and / or b) a polysiloxane-polycarbonate copolymer;
c) A thermoplastic composition containing a metal (oxy) hydroxide having a BET surface area of at least 10 measured according to DIN ISO 9277: 2010.   The thermoplastic composition according to claim 1, wherein the silicon-containing rubber a2) is a graft copolymer containing a silicon-containing elastomer component. The metal (oxy) hydroxide c) is a compound represented by the general formula M _a (OH) _b or M _a O (OH) _b , wherein M is Li, Na, K, Mg, Ca 3. The thermoplastic composition according to claim 1, wherein the thermoplastic composition is selected from the group consisting of Al, Zn, and Fe, a is 1 or 2, and b is 1, 2 or 3. 3. The metal (oxy) hydroxide c) is a metal oxyhydroxide represented by the general formula M _a O (OH) _b , preferably AlO (OH), preferably γ-AlO (OH). 4. The thermoplastic composition according to any one of items 1 to 3.   The composition further comprises d) a flame retardant, preferably a flame retardant selected from alkali or alkaline earth sulfonates, sulfonamides, perfluoroborate, halogenated compounds and phosphorus-containing organic compounds. The thermoplastic composition according to any one of 1 to 4.   The composition further comprises e) copper-containing spinels such as copper chromium oxide spinel, copper molybdenum oxide spinel and copper chromium manganese oxide spinel; tin antimony oxide, tin bismuth oxide, tin aluminum oxide and tin molybdenum oxide The thermoplastic composition as described in any one of Claim 1 to 5 containing the metal oxide selected from tin containing oxides, such as. Wherein the composition further, _f) TiO 2, ZnO and the thermoplastic composition according to any one of 6 claim 1 containing a white pigment selected from BaSO _4.   The thermoplastic composition according to any one of claims 1 to 7, wherein the thermoplastic resin a) is a polycarbonate-based resin. The thermoplastic composition is
a) a1) 50 to 98% by weight of thermoplastic resin, a2) 1 to 20% by weight of Si-containing rubber,
b) 0 to 48% polysiloxane-polycarbonate copolymer;
c) 1-20% by weight of a metal (oxy) hydroxide,
d) 0-15 wt% flame retardant,
e) 0 to 25% by weight of metal oxide,
_f) TiO 2, ZnO and BaSO ₄ thermoplastic composition according to any one of claims 1 to 8 containing a white pigment 0-25% by weight selected from.   The thermoplastic composition according to any one of the preceding claims, wherein the molded part of the composition is 1.6 mm thick and is UL94 grade V2, preferably grade V1, more preferably grade V0.   A molded part comprising the thermoplastic composition according to any one of claims 1 to 10. Preparing a molded part according to claim 11; irradiating a region of the part where the conductive path is to be formed with laser light; and subsequently metallizing the irradiated area;
The thermoplastic resin composition comprises 1 to 25% by weight of e) copper-containing spinels such as copper chromium oxide spinel, copper molybdenum oxide spinel and copper chromium manganese oxide spinel; tin antimony oxide, tin bismuth oxide, A method for producing a circuit board, comprising a tin-containing oxide such as tin aluminum oxide and tin molybdenum oxide.   A circuit board obtainable by the method according to claim 12.   Use of a metal (oxy) hydroxide having a BET surface area of at least 10 measured according to DIN ISO 9277: 2010, for improving flame retardancy in a thermoplastic composition containing a thermoplastic resin and a Si-containing rubber.   Use of a metal (oxy) hydroxide as an improvement in hydrolysis stability in a thermoplastic composition containing a thermoplastic resin and a Si-containing rubber.